CN104986898B - A kind of method and device of normal temperature ferrite circular treatment heavy metal containing sewage - Google Patents
A kind of method and device of normal temperature ferrite circular treatment heavy metal containing sewage Download PDFInfo
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Abstract
The invention discloses a kind of method and device of normal temperature ferrite circular treatment heavy metal containing sewage, the described method comprises the following steps：S1, first adds green vitriol in sewage, aerobic under normal temperature to stir；Add NaOH, 15~30min of isolation air stirring；S2, then carries out natural subsidence by sewage, after sedimentation, carries out separation of solid and liquid；S3, after separation of solid and liquid, supernatant liquor discharge, lower floor's sludge takes out standby；S4, adds NaOH in described sludge, and stirs 15min in atmosphere, obtains magnetic sludge；S5, during the green vitriol in the magnetic sludge and step S1 together added into sewage.The present invention disposably can effectively remove the contents of many kinds of heavy metal ion in sewage at normal temperatures, and the reaction time is short, and draining water quality is high, and the sludge in cyclic process has magnetic, and magnetic sludge recoverable.
Description
Technical field
The present invention relates to a kind of method and device of normal temperature ferrite circular treatment heavy metal containing sewage, belong to heavy metal containing sewage
Process field.
Background technology
China's heavy metal pollution of water body problem is very prominent, develops into social concern via environmental problem.With environment
It is required that improving, national, plating, the drainage requirement of semiconductor, mine industry more and more stricter for heavy metal containing sewage discharge standard
Also more and more higher, it is therefore desirable to develop new technique, the environmental protection standard that satisfaction is increasingly improved.
Conventional heavy metal containing sewage processing mode has at present：Chemical precipitation method, hyperfiltration, ion-exchange and absorption method
Deng.Wherein, chemical precipitation method is the simplest ripe, but precipitation removal efficiency is easily influenceed by many factors, effect
It is unstable；Traditional ferrite circular treatment method operation temperature is at 70 DEG C, and observable index is higher, while Effluent criteria is relatively low, and produces
The substantial amounts of sludge of life, sludge needs advanced treating.Reverse-osmosis treated method needs to carry out strict pretreatment, and treatment effect is preferable,
But it is relatively costly.Ion-exchange is that heavy metal ion is swapped with ion-exchanger, reach removal heavy metal in waste water from
The method of son, processing capacity is big, and effluent quality is good, recyclable heavy metal resources, to environment non-secondary pollution, but ion-exchanger
Oxidizable failure, regeneration is frequent, and operating cost is high.Absorption method be using heavy metal in porous solid material Adsorption water from
A kind of effective ways of son, the key of technique is adsorbent, a lot, the conventional active charcoals of the species of adsorbent, but activated carbon
Price is high, and service life is short, needs regeneration, and operating cost is high.Therefore currently it is badly in need of a kind of new heavy metal-polluted water technology to come
Solve the above problems.
The content of the invention
It is an object of the present invention to provide a kind of method and device of normal temperature ferrite circular treatment heavy metal containing sewage, it
Problems of the prior art can effectively be solved, especially traditional ferrite circular treatment method operation temperature at 70 DEG C,
Observable index is higher, while Effluent criteria is relatively low, and the substantial amounts of sludge of generation needs to carry out the problem of advanced treating.
In order to solve the above technical problems, the present invention is adopted the following technical scheme that：A kind of normal temperature ferrite circular treatment weight
The method of metal sewage, comprises the following steps：
S1, first adds green vitriol in sewage, it is aerobic under normal temperature stir (time be no more than 2 minutes, stir
Mix uniform)；Add NaOH, 15~30min of isolation air stirring；
S2, then carries out natural subsidence by sewage, after sedimentation, carries out separation of solid and liquid；
S3, after separation of solid and liquid, supernatant liquor discharge, lower floor's sludge takes out standby；
S4, adds NaOH in described sludge, and stirs 15min in atmosphere, obtains magnetic sludge；
S5, during the green vitriol in the magnetic sludge and step S1 together added into sewage.
Preferably, in step S1, NaOH is added, completely cuts off air stirring 30min, such that it is able to more effectively go decontamination
Heavy metal in water.
Preferably, in step S1, total heavy metal quality in sewage：Green vitriol quality=1:12~25, utilize
The proportioning simultaneously determines the addition of medicine according to heavy metal ion total amount in water, not only wastewater treatment efficiency preferably, Er Qiesheng
Produce cost relatively low.
Preferably, in step S1, when treatment for the first time is carried out to sewage, the quality of the NaOH of addition is seven hydration sulphur
6~7 times of sour ferrous iron quality, the dosage of NaOH are determined according to the qualifications, such that it is able to reach preferable sewage
Contents of many kinds of heavy metal ion in treatment effect, effectively removal sewage, while treatment effeciency is higher.
It is furthermore preferred that in step S1, when treatment for the first time is carried out to sewage, the quality of the NaOH of addition is seven hydrations
6.4 times of ferrous sulfate quality, such that it is able to reach more preferable wastewater treatment efficiency, the various heavy effectively in removal sewage
Ion, while treatment effeciency is higher.
In step S4 of the invention, the quality of the NaOH of addition is the NaOH quality of addition in step S1
70%~80%, the dosage of NaOH in later stage sewage disposal process is determined according to the condition, such that it is able to reach preferably
Wastewater treatment efficiency.
Preferably, when continuous circular treatment n-th, the quality of the green vitriol added in step S1 is N-
At 1 time 80%~90%, when the quality of the NaOH of addition is the N-1 times 70%~80%, wherein, N >=2, so that
The contents of many kinds of heavy metal ion in sewage disposably can be effectively removed, the simultaneous reactions time is shorter, and treatment effeciency is higher, and cost
It is lower.
In step S2 of the invention, sewage is carried out into natural subsidence 24h, in the case of conditions permit, natural subsidence can
To save the energy resource consumption that artificial or machine is separate；Of course for improve production efficiency, it would however also be possible to employ magnetic drum seperator or its
He is processed centrifugation apparatus.
In the method for foregoing normal temperature ferrite circular treatment heavy metal containing sewage, also include：S0, under normal temperature condition, in dirt
Calcium hydroxide is added in water carries out neutralization pretreatment so that the pH value of sewage is 5~8, such that it is able to reduce treatment later stage hydroxide
The addition of sodium, using the relatively low calcium hydroxide of price, can save part spending；In addition, also certain sterilizing
Effect；Further, it is also possible to play the solidifying effect that helps to the colloidal particles of waste water, and as granular core weighting agent, contribute to insoluble
The separation of thing.
In the above method, described sewage is the dirt containing one or more ions in Cu, Zn, Cr, Ni, Cd or Pb
Water.
The device of the normal temperature ferrite circular treatment heavy metal containing sewage of preceding method is realized, including：Reaction unit, precipitation dress
Put, filter and dehydration device, reactive tank and mixing channel are provided with described reaction unit, precipitation is provided with settler
Groove, is provided with lautertuns in filter, described reactive tank is connected with mixing channel and stillpot respectively, stillpot respectively with filtering
The connection of groove, mixing channel and dehydration device.
Preferably, described reaction unit uses the stainless steel cauldron of model 5000, settler to use model
The horizontal spiral discharge sedimentation centrifuge of LW-350, filter uses the filtering screening machine of model XZS-450, not only cost
It is low, and the removing speed of heavy metal ions in sewage is higher.
Compared with prior art, the present invention has advantages below：
1st, the heavy metal containing sewage that the industries such as plating, mine are produced can be processed, disposably can be effectively gone under normal temperature
Except the contents of many kinds of heavy metal ion in sewage, the problem of high energy consumption during ferrite oxidative treatment is effectively overcome, while instead
Short between seasonable, floor space is small；
2nd, with the increase of cycle-index, the rate of settling of sludge is gradually accelerated, and treatment effeciency is stepped up；
3rd, sedimentation rate is low, and sludge yield is low；
4th, the heavy metal in sewage can be effectively removed, draining water quality is high, and the sewage PH after treatment, content of beary metal are up to standard
(refer to integrated wastewater discharge standard GB8978-1996), clearance is up to more than 94%；
5th, there is magnetic, and magnetic sludge recoverable in the sludge in cyclic process, such as be used as catalyst；
6th, it is of the invention from the PH in sewage disposal process, heavy metal ion content and effect of settling, by adjusting hydrogen
Sodium oxide molybdena, the consumption of green vitriol and adjustment mixing time, make the moisture content of magnetic sludge, the rate of settling, purity,
Utilizability can obtain largest optimization, so that the heavy metal ion eliminated in sewage of maximal efficiency；
7th, the magnetic sludge in the present invention can be recycled and reused, so as to reduce cost of sewage disposal；
8th, cost of sewage disposal is relatively low, and treatment agent wide material sources；
9th, the present invention uses ferrous ion and part trivalent, ferrite is generated in the basic conditions, by the weight in sewage
Metal ion entrainment removing；Using sedimentation or Magnetic Isolation, sludge is re-used for sewage disposal, such that it is able to greatly improve dirt
The rate of settling of mud, and then improve the removing speed of heavy metal ions in sewage.
Brief description of the drawings
Fig. 1 is wastewater treatment experiment flow figure；
Fig. 2 is the X-ray diffraction material phase analysis of the sludge settling thing of embodiment 1；
Fig. 3 is the multiple circular treatment rate of settling schematic diagram of embodiment 2；
Fig. 4 is the measurement result schematic diagram of the sedimentation rate of embodiment 2；
Fig. 5 is device connection diagram of the invention.
Reference：1- reaction units, 2- settlers, 3- filters, 4- dehydration devices, 5- reactive tanks, 6- mixing
Groove, 7- stillpots, 8- lautertuns.
The present invention is further illustrated with reference to the accompanying drawings and detailed description.
Specific embodiment
Embodiment 1：A kind of method of normal temperature ferrite circular treatment heavy metal containing sewage, as shown in figure 1, including following step
Suddenly：
S1, it is sewage (the described dirt of 50mg/L that 0.75g green vitriols are added into 600mL, heavy metal total content
Water is the sewage containing Cu, Zn, Cr and Ni ion) in, it is aerobic under normal temperature to stir (no more than 2min)；Add
131.25ml, molar concentration are the sodium hydroxide solution of 1mol/L, isolation air stirring 30min；
S2, then carries out natural subsidence 24h by sewage, after sedimentation, carries out separation of solid and liquid；
S3, after separation of solid and liquid, the sludge of lower floor 100ml is taken out standby by supernatant liquor (i.e. sewage) discharge；
S4, the sewage 600ml that heavy metal ion content is 50mg/L is added in described sludge, and (amount of sewage is by including
Total ion concentration determine, but, also require that sewage ion concentration is not less than 50mg/L) and 91.88ml, molar concentration be 1mol/L
Sodium hydroxide solution, and aerobic stirring 15min, obtain magnetic sludge；
S5, during the green vitriol in the magnetic sludge and step S1 together added into sewage；(start the 2nd
Circular treatment, now, it is necessary to add 0.65g green vitriols in sewage in step S1, aerobic stirring is equal under normal temperature
It is even；105ml, molar concentration are added for 1mol/L sodium hydroxide solutions, isolation air stirring 30min；Then sewage is carried out
Natural subsidence 24h, after sedimentation, carries out separation of solid and liquid；Supernatant liquor (i.e. sewage) is discharged) supernatant liquor (i.e. sewage) now is dense
Degree is up to standard, as shown in table 1 below (when wherein, second circulation starts, partly process qualified sewage and excluded, remaining dirt
Heavy metal total content has been less than 50mg/L (to contain sludge) in water；But the sewage relevant parameter in second circulation in step S1 is not
Need to change, ionic weight is ignored herein reduces influence to embodiment slightly).
The device of the normal temperature ferrite circular treatment heavy metal containing sewage of the above method is realized, as shown in figure 5, including：Reaction
Device 1, settler 2, filter 3 and dehydration device 4, are provided with reactive tank 5 and mixing channel 6 in described reaction unit 1, sink
Stillpot 7 is provided with shallow lake device 2, lautertuns 8 is provided with filter 3, described reactive tank 5 respectively with mixing channel 6 and precipitation
Groove 7 is connected, and stillpot 7 is connected with lautertuns 8, mixing channel 6 and dehydration device 4 respectively.Described reaction unit 1 can use model
It is 5000 stainless steel cauldron, settler 2 can be using the horizontal spiral discharge sedimentation centrifuge of model LW-350, filtering
Device 3 can be using the filtering screening machine of model XZS-450.
Table 1
Additionally, the sludge in cyclic process is implicitly present in magnetic, wherein, magnetisable material Fe3O4Material phase analysis such as Fig. 2 institutes
Show.
Embodiment 2：A kind of method of normal temperature ferrite circular treatment heavy metal containing sewage, as shown in figure 1, including following step
Suddenly：
S1, by 0.75g green vitriols add 600ml, containing heavy metal Cu for 50mg/L sewage in, have under normal temperature
Oxygen stirs；Add the NaOH that 131.25ml, molal weight are 1mol/L, isolation air stirring 30min；
S2, then carries out natural subsidence 24h by sewage, after sedimentation, carries out separation of solid and liquid；
S3, after separation of solid and liquid, the sludge of lower floor 100ml is taken out standby by supernatant liquor (i.e. sewage) discharge；
S4,500ml is added in described sludge, is the sewage and 91.88ml, molal weight of 10mg/L containing heavy metal Cu
It is the sodium hydroxide solution of 1mol/L, and aerobic stirring 15min, obtain magnetic sludge；
S5, during the green vitriol in the magnetic sludge and step S1 together added into sewage；(start the 2nd
Circular treatment, now, it is necessary to add 0.65g green vitriols in sewage in step S1, aerobic stirring is equal under normal temperature
It is even；Add the sodium hydroxide solution that 105ml, molal weight are 1mol/L, isolation air stirring 30min；Then sewage is entered
Row natural subsidence 24h, after sedimentation, carries out separation of solid and liquid；Supernatant liquor (i.e. sewage) is discharged, and the sludge of lower floor 100ml is taken out
It is standby, add 500ml, be the sewage of 10mg/L and the sodium hydroxide solution of 6.4ml, and aerobic stirring containing heavy metal Cu
15min, obtains magnetic sludge；During green vitriol in the magnetic sludge and step S1 together added into sewage；So follow
Ring 5 times, wherein, the quality of the NaOH added in step S4 is the NaOH quality added in step S1 in this time circulating
70%~80%；And when continuous circular treatment n-th, the quality of the green vitriol added in step S1 is N-
At 1 time 80%~90%, when the quality of the NaOH of addition is the N-1 times 70%~80%, wherein, N >=2)
The device of the normal temperature ferrite circular treatment heavy metal containing sewage of the above method is realized, as shown in figure 5, including：Reaction
Device 1, settler 2, filter 3 and dehydration device 4, are provided with reactive tank 5 and mixing channel 6 in described reaction unit 1, sink
Stillpot 7 is provided with shallow lake device 2, lautertuns 8 is provided with filter 3, described reactive tank 5 respectively with mixing channel 6 and precipitation
Groove 7 is connected, and stillpot 7 is connected with lautertuns 8, mixing channel 6 and dehydration device 4 respectively.
Method according to embodiment 2 circulates continuous processing sewage 5 times, after tested, with the increase of cycle-index, sludge
The rate of settling is gradually increasing, as shown in figure 3, sedimentation rate is not superimposed, the simply increase of a small range, and as shown in Figure 4；Together
When, the sewage PH value and Cu contents after treatment are up to standard.
From the PH in experimentation, heavy metal ion content and effect of settling, by adjusting NaOH, seven hydrations
The consumption of ferrous sulfate, adjusts mixing time and speed, enables moisture content, the rate of settling, purity, the utilizability of magnetic sludge
Obtain largest optimization.
Embodiment 3：A kind of method of normal temperature ferrite circular treatment heavy metal containing sewage, as shown in figure 1, including following step
Suddenly：
S0, under normal temperature condition, sewage (sewage be containing Cu, Zn, Cr, Ni, Cd or Pb in one or more materials
Sewage) in add calcium hydroxide carry out neutralization pretreatment so that the pH value of sewage be 5~8；
S1, during 0.8g green vitriols are added into 833ml, content of beary metal for the sewage of 80mg/L, has under normal temperature
Oxygen stirs；Add the sodium hydroxide solution that 120ml, molal weight are 1mol/L, isolation air stirring 15min；
S2, then carries out natural subsidence 24h by sewage, after sedimentation, carries out separation of solid and liquid；
S3, after separation of solid and liquid, supernatant liquor (i.e. sewage) discharge, lower floor's sludge takes out standby；
S4, it is the sodium hydroxide solution of 1mol/L to add 96ml, molal weight in described sludge, and is stirred in atmosphere
15min is mixed, magnetic sludge is obtained；
S5, during the green vitriol in the magnetic sludge and step S1 together added into sewage, goes to S1, wherein,
When continuous circular treatment n-th, when the quality of the green vitriol added in step S1 is the N-1 times 80%, plus
When the quality of the NaOH for entering is the N-1 times 70%, wherein, N >=2.
The device of the normal temperature ferrite circular treatment heavy metal containing sewage of the above method is realized, as shown in figure 5, including：Reaction
Device 1, settler 2, filter 3 and dehydration device 4, are provided with reactive tank 5 and mixing channel 6 in described reaction unit 1, sink
Stillpot 7 is provided with shallow lake device 2, lautertuns 8 is provided with filter 3, described reactive tank 5 respectively with mixing channel 6 and precipitation
Groove 7 is connected, and stillpot 7 is connected with lautertuns 8, mixing channel 6 and dehydration device 4 respectively.
Embodiment 4：A kind of method of normal temperature ferrite circular treatment heavy metal containing sewage, as shown in figure 1, including following step
Suddenly：
S0, under normal temperature condition, sewage (sewage be containing Cu, Zn, Cr, Ni, Cd or Pb in one or more materials
Sewage) in add calcium hydroxide carry out neutralization pretreatment so that the pH value of sewage be 5~8；
S1, during 1.0g green vitriols are added into 500ml, content of beary metal for the sewage of 100mg/L, has under normal temperature
Oxygen stirs；Add the sodium hydroxide solution that 160ml, molal weight are 1mol/L, isolation air stirring 20min；
S2, then carries out natural subsidence 24h by sewage, after sedimentation, carries out separation of solid and liquid；
S3, after separation of solid and liquid, supernatant liquor (i.e. sewage) discharge, lower floor's sludge takes out standby；
S4, it is the sodium hydroxide solution of 1mol/L that 120ml, molal weight are added in described sludge, and in atmosphere
Stirring 15min, obtains magnetic sludge；
S5, during the green vitriol in the magnetic sludge and step S1 together added into sewage, goes to S1, wherein,
When continuous circular treatment n-th, when the quality of the green vitriol added in step S1 is the N-1 times 90%, plus
When the quality of the NaOH for entering is the N-1 times 75%, wherein, N >=2.
The device of the normal temperature ferrite circular treatment heavy metal containing sewage of the above method is realized, as shown in figure 5, including：Reaction
Device 1, settler 2, filter 3 and dehydration device 4, are provided with reactive tank 5 and mixing channel 6 in described reaction unit 1, sink
Stillpot 7 is provided with shallow lake device 2, lautertuns 8 is provided with filter 3, described reactive tank 5 respectively with mixing channel 6 and precipitation
Groove 7 is connected, and stillpot 7 is connected with lautertuns 8, mixing channel 6 and dehydration device 4 respectively.
A kind of operation principle of embodiment of the invention：Heavy metal containing sewage adds reaction unit 1 with green vitriol
In reactive tank 5 in reacted, while mixing channel 6 in reaction unit 1 adds basic agent, then flowed into by mixing channel 6
Reactive tank 5 is reacted；After reaction, sewage flow in the stillpot 7 in settler 2 and carries out natural subsidence, after separation of solid and liquid,
Supernatant liquor is discharged through the lautertuns 8 in filter 3, and lower floor's sludge is recycled in mixing channel 6, is mixed with the basic agent for adding
After conjunction, as magnetic sludge, add and reacted with sewage, green vitriol in reactive tank 5, repeat said process；
If the lower floor's sludge for producing is more, a part can be recycled in mixing channel 6, unnecessary returns after the squeezing of dehydration device 4
Receive.
Claims (8)
1. a kind of method of normal temperature ferrite circular treatment heavy metal containing sewage, it is characterised in that described sewage be containing Cu,
The sewage of one or more ions in Zn, Cr, Ni, Cd or Pb, comprises the following steps：
S1, first adds green vitriol in sewage, aerobic under normal temperature to stir；NaOH is added, isolation is empty
15~30min of gas agitating, wherein, total heavy metal quality in sewage：Green vitriol quality=1:12~25；
S2, then carries out natural subsidence by sewage, after sedimentation, carries out separation of solid and liquid；
S3, after separation of solid and liquid, supernatant liquor discharge, lower floor's sludge takes out standby；
S4, adds NaOH in described sludge, and stirs 15min in atmosphere, obtains magnetic sludge；
S5, during the green vitriol in the magnetic sludge and step S1 together added into sewage.
2. the method for normal temperature ferrite circular treatment heavy metal containing sewage according to claim 1, it is characterised in that step S1
In, when treatment for the first time is carried out to sewage, the quality of the NaOH of addition is 6~7 times of green vitriol quality.
3. the method for normal temperature ferrite circular treatment heavy metal containing sewage according to claim 2, it is characterised in that step S4
The quality of the NaOH of middle addition is the 70%~80% of the NaOH quality of addition in step S1.
4. the method for normal temperature ferrite circular treatment heavy metal containing sewage according to claim 3, it is characterised in that when continuous
During circular treatment n-th, when the quality of the green vitriol added in step S1 is the N-1 times 80%~90%, plus
When the quality of the NaOH for entering is the N-1 times 70%~80%, wherein, N >=2.
5. the method for normal temperature ferrite circular treatment heavy metal containing sewage according to claim 1, it is characterised in that step S2
In, sewage is carried out into natural subsidence 24h.
6. the method for the normal temperature ferrite circular treatment heavy metal containing sewage according to any one of Claims 1 to 5, its feature exists
In also including：S0, under normal temperature condition, in sewage add calcium hydroxide carry out neutralization pretreatment so that the pH value of sewage be 5~
8。
7. the device of the normal temperature ferrite circular treatment heavy metal containing sewage of claim 1~6 any one methods described is realized, it is special
Levy and be, including：Reaction unit (1), settler (2), filter (3) and dehydration device (4), described reaction unit
(1) reactive tank (5) and mixing channel (6) are provided with, stillpot (7) is provided with settler (2), filter was provided with (3)
Filter pocket (8), described reactive tank (5) is connected with mixing channel (6) and stillpot (7) respectively, stillpot (7) respectively with lautertuns
(8), mixing channel (6) and dehydration device (4) are connected.
8. the device of normal temperature ferrite circular treatment heavy metal containing sewage according to claim 7, it is characterised in that described
Reaction unit (1) uses the stainless steel cauldron of model 5000, settler (2) to use the horizontal spiral of model LW-350
Discharging sedimentation centrifuge, filter (3) uses the filtering screening machine of model XZS-450.
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| CN110255806A (en) * | 2019-07-05 | 2019-09-20 | 南京中微纳米功能材料研究院有限公司 | A kind of sewage device of ferrite dynamic film process heavy metal |
| CN111453880A (en) * | 2020-04-09 | 2020-07-28 | 安徽浩悦环境科技有限责任公司 | Method for removing waste liquid containing various heavy metals by combined precipitation method |
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